


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813031255/vn2078sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536813031255/vn2078Isup2.hkl |
![]() | Chemdraw file https://doi.org/10.1107/S1600536813031255/vn2078Isup3.cdx |
CCDC reference: 971936
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.064
- Data-to-parameter ratio = 18.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2A ... Please Check PLAT976_ALERT_2_C Negative Residual Density at 1.09A from N2 . -0.41 eA-3
Alert level G PLAT004_ALERT_5_G Polymeric Structure Found with Dimension ....... 2 Info PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Why ? PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 2 Do ! N1 -CD1 -S1 -C1 -121.10 0.90 8.455 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 6 Do ! CD1 -N1 -C1 -S1 122.00 17.00 7.656 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 7 Do ! CD1 -S1 -C1 -N1 -147.00 17.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 10 Do ! N2 -CD1 -N2 -C2 123.90 0.20 2.655 1.555 1.555 1.555 PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.25 Ratio PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) ..... 1 Why ? PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 2
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 2 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
To 25 ml of an aqueous solution of thiocyanic acid (0.4 mol.l-1) prepared using the published procedure (Bartlett et al., 1969) an appropriate amount of cadmium carbonate (0.832 g, 5 mmol) was added and refluxed for 2 h. After cooling, 25 ml of methanol and 0.7 ml of a solution of 1,3-phenylenediamine (7.5 mol.l-1) was added. The resulting solution was heated under reflux for 2 h and left at ambient temperature for 2 hours after which well shaped brown crystals were obtained on slow evaporation of the solvent. They were washed with diethyl ether and dried over P2O5.
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.98 Å, N—H = 0.92 Å, and with Uiso(H) = 1.2Ueq(C, N).
Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).
[Cd(NCS)2(C6H8N2)2] | F(000) = 656 |
Mr = 336.7 | Dx = 1.996 Mg m−3 Dm = 1.931 Mg m−3 Dm measured by Flotation |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1283 reflections |
a = 10.8704 (6) Å | θ = 3.2–27.5° |
b = 12.8983 (10) Å | µ = 2.29 mm−1 |
c = 8.3362 (5) Å | T = 150 K |
β = 106.503 (3)° | Prism, brown |
V = 1120.67 (13) Å3 | 0.17 × 0.07 × 0.06 mm |
Z = 4 |
Bruker APEXII diffractometer | 1130 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 27.5°, θmin = 3.2° |
CCD rotation images, thin slices scans | h = −10→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | k = −16→16 |
Tmin = 0.825, Tmax = 0.872 | l = −10→9 |
4396 measured reflections | 2 standard reflections every 120 min |
1283 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0156P)2] where P = (Fo2 + 2Fc2)/3 |
1283 reflections | (Δ/σ)max < 0.001 |
70 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[Cd(NCS)2(C6H8N2)2] | V = 1120.67 (13) Å3 |
Mr = 336.7 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.8704 (6) Å | µ = 2.29 mm−1 |
b = 12.8983 (10) Å | T = 150 K |
c = 8.3362 (5) Å | 0.17 × 0.07 × 0.06 mm |
β = 106.503 (3)° |
Bruker APEXII diffractometer | 1283 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | 1130 reflections with I > 2σ(I) |
Tmin = 0.825, Tmax = 0.872 | Rint = 0.061 |
4396 measured reflections | 2 standard reflections every 120 min |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.60 e Å−3 |
1283 reflections | Δρmin = −0.58 e Å−3 |
70 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.5 | 0.20749 (3) | 0.25 | 0.01462 (12) | |
S1 | 0.65559 (10) | 0.05195 (8) | 0.40889 (13) | 0.0297 (3) | |
N1 | 0.8532 (3) | 0.1670 (2) | 0.6240 (4) | 0.0219 (7) | |
C1 | 0.7707 (3) | 0.1202 (3) | 0.5352 (4) | 0.0163 (8) | |
N2 | 0.6151 (3) | 0.2057 (2) | 0.0483 (4) | 0.0191 (7) | |
H2A | 0.6952 | 0.233 | 0.0968 | 0.023* | |
H2B | 0.6263 | 0.1377 | 0.0223 | 0.023* | |
C2 | 0.5594 (3) | 0.2606 (3) | −0.1055 (4) | 0.0159 (8) | |
C3 | 0.5 | 0.2075 (4) | −0.25 | 0.0149 (10) | |
H3 | 0.5 | 0.1339 | −0.25 | 0.018* | |
C4 | 0.5598 (3) | 0.3684 (3) | −0.1044 (4) | 0.0174 (8) | |
H4 | 0.6007 | 0.4054 | −0.0049 | 0.021* | |
C5 | 0.5 | 0.4211 (4) | −0.25 | 0.0237 (13) | |
H5 | 0.5 | 0.4947 | −0.25 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0134 (2) | 0.0146 (2) | 0.0142 (2) | 0 | 0.00127 (14) | 0 |
S1 | 0.0252 (6) | 0.0127 (5) | 0.0371 (6) | −0.0027 (4) | −0.0140 (4) | 0.0019 (4) |
N1 | 0.0209 (18) | 0.0165 (17) | 0.0248 (18) | 0.0001 (14) | 0.0010 (15) | 0.0012 (14) |
C1 | 0.0176 (19) | 0.0127 (19) | 0.0180 (19) | 0.0044 (16) | 0.0041 (15) | 0.0024 (15) |
N2 | 0.0182 (16) | 0.0191 (17) | 0.0199 (17) | 0.0006 (14) | 0.0051 (13) | −0.0011 (14) |
C2 | 0.0117 (18) | 0.021 (2) | 0.0168 (19) | 0.0008 (15) | 0.0067 (15) | 0.0013 (15) |
C3 | 0.013 (2) | 0.012 (3) | 0.020 (3) | 0 | 0.006 (2) | 0 |
C4 | 0.0166 (19) | 0.018 (2) | 0.0175 (19) | −0.0036 (15) | 0.0046 (15) | −0.0055 (15) |
C5 | 0.028 (3) | 0.010 (3) | 0.036 (3) | 0 | 0.014 (3) | 0 |
Cd1—N1i | 2.306 (3) | N2—H2A | 0.92 |
Cd1—N1ii | 2.306 (3) | N2—H2B | 0.92 |
Cd1—N2iii | 2.364 (3) | C2—C3 | 1.376 (4) |
Cd1—N2 | 2.364 (3) | C2—C4 | 1.391 (5) |
Cd1—S1iii | 2.7143 (10) | C3—C2iv | 1.376 (4) |
Cd1—S1 | 2.7143 (10) | C3—H3 | 0.95 |
S1—C1 | 1.643 (4) | C4—C5 | 1.382 (4) |
N1—C1 | 1.157 (4) | C4—H4 | 0.95 |
N1—Cd1i | 2.306 (3) | C5—C4iv | 1.382 (4) |
N2—C2 | 1.439 (4) | C5—H5 | 0.95 |
N1i—Cd1—N1ii | 90.81 (15) | C2—N2—Cd1 | 117.1 (2) |
N1i—Cd1—N2iii | 96.91 (10) | C2—N2—H2A | 108 |
N1ii—Cd1—N2iii | 83.89 (11) | Cd1—N2—H2A | 108 |
N1i—Cd1—N2 | 83.89 (11) | C2—N2—H2B | 108 |
N1ii—Cd1—N2 | 96.91 (10) | Cd1—N2—H2B | 108 |
N2iii—Cd1—N2 | 178.87 (14) | H2A—N2—H2B | 107.3 |
N1i—Cd1—S1iii | 174.75 (8) | C3—C2—C4 | 120.2 (4) |
N1ii—Cd1—S1iii | 92.41 (8) | C3—C2—N2 | 120.6 (3) |
N2iii—Cd1—S1iii | 87.56 (8) | C4—C2—N2 | 119.1 (3) |
N2—Cd1—S1iii | 91.60 (8) | C2—C3—C2iv | 120.4 (5) |
N1i—Cd1—S1 | 92.41 (8) | C2—C3—H3 | 119.8 |
N1ii—Cd1—S1 | 174.75 (8) | C2iv—C3—H3 | 119.8 |
N2iii—Cd1—S1 | 91.60 (8) | C5—C4—C2 | 119.0 (4) |
N2—Cd1—S1 | 87.56 (8) | C5—C4—H4 | 120.5 |
S1iii—Cd1—S1 | 84.68 (4) | C2—C4—H4 | 120.5 |
C1—S1—Cd1 | 99.92 (12) | C4iv—C5—C4 | 121.2 (5) |
C1—N1—Cd1i | 165.4 (3) | C4iv—C5—H5 | 119.4 |
N1—C1—S1 | 178.8 (3) | C4—C5—H5 | 119.4 |
N1i—Cd1—S1—C1 | 6.69 (14) | S1iii—Cd1—N2—C2 | 81.6 (2) |
N1ii—Cd1—S1—C1 | −121.1 (9) | S1—Cd1—N2—C2 | 166.2 (2) |
N2iii—Cd1—S1—C1 | −90.29 (14) | Cd1—N2—C2—C3 | −103.9 (3) |
N2—Cd1—S1—C1 | 90.47 (15) | Cd1—N2—C2—C4 | 72.5 (3) |
S1iii—Cd1—S1—C1 | −177.70 (14) | C4—C2—C3—C2iv | 0.0 (2) |
Cd1i—N1—C1—S1 | 122 (17) | N2—C2—C3—C2iv | 176.3 (3) |
Cd1—S1—C1—N1 | −147 (17) | C3—C2—C4—C5 | 0.0 (4) |
N1i—Cd1—N2—C2 | −101.1 (2) | N2—C2—C4—C5 | −176.4 (3) |
N1ii—Cd1—N2—C2 | −11.0 (3) | C2—C4—C5—C4iv | 0.0 (2) |
N2iii—Cd1—N2—C2 | 123.9 (2) |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, y, −z+1/2; (iv) −x+1, y, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···S1v | 0.92 | 2.67 | 3.589 (3) | 173 |
Symmetry code: (v) x, −y, z−1/2. |
The crystal engineering of inorganic-organic hybrid coordination polymers is currently one of the most active fields in coordination chemistry, supramolecular and materials chemistry. These compounds attract significant attention for their architectures and topologies (Yang et al., 2001), including a large number of extended assemblies such as helical network (Withersby et al., 1997; Chemli et al. 2013) molecular zippers, diamondoid, honeycomb (Tong et al., 1998), square- grid (MacGillivary et al., 1994), T-shaped and ladder frameworks. (Fujita et al., 1995; Blake et al.,1997). Hybrid inorganic-organic thiocyanate materials exhibit interesting physical properties such electrical conductivity and dielectric relaxation process (Karoui et al., 2013) and may have potential applications in non-linear optics and luminescence (Chen et al., 2000; Bai et al., 2011). Herein we report the structure of a new polymeric hybrid [Cd(SCN)2(C6H8N2)2]n. As shown in Fig. 1, each cadmium atom, which sits on a twofold rotation axis, is coordinated by two cis N-bonded and two cis S-bonded thiocyanato anions. Two trans-coordinated neutral m-phenylenediamine ligands complete the octahedral coordination geometry around cadmium. The crystal structure of the title compound consists of both doubly µ-1,3-SCN and µ-1,3-phenylendiamine –bridged two-dimensional networks (Fig. 2). In the CdN4S2 core, the Cd—N and Cd—S bonds are in the range 2.3061 - 2.364 (3) Å and 2.7143 (10) Å, respectively (Table 1). The bond angles involving the cadmium (II) atom range from 83.89 (11) to 96.91 (10)° and from 174.75 (8) to 178.87 (14)°. These values are in good agreement with those observed in other similar complexes (Chemli et al. 2013). The double SCN bridging mode gives rise to a centrosymmetrical eight-membered Cd(SCN)2Cd rings in a chair conformation because of the almost linear SCN groups (S–C–N angle = 178.8 (3)°). The distance between adjacent Cd atoms in Cd2 (SCN)2 rings is 5.937 Å. Again, these rings built up a staircase-like chain through their corner-sharing action at the two cadmium atoms via the µ-1,3-phenylenediamine moiety and give rise to twenty-membered [Cd4(µ-1,3-SCN)4(µ-1,3-phenylendiamine)2] macrocycles as subunits, as depicted in Fig. 2. The bond angles in the phenyl groups deviate significantly from the idealized value of 120° due to the effect of the substituent. In fact, it was established that the angular deformations of phenyl groups can be described as a sum of the effects of the different substituents (Domenicano & Murray-Rust, 1979). The phenyl rings of 1,3-phenylendiamine ligand are planar with the greatest deviation from the six-atoms least-square plane of 0.0001 Å. They are well ordered with C–C–C angles in agreement with the expected sp2 hybridization. The π-π interactions between neighboring phenyl rings may be neglected (>4 Å). The major contributions of the cohesion and the stability of this polymeric structure is assured by the covalent Cd-(S,N) bonds and the presence of one weak intralayer N–H···S hydrogen bond with the H···S and N···S distances of 2.674 Å and 3.589 (3) Å, respectively (Table 2).